JPH0791504B2 - One component primer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a one-component primer that can be used for steel structures.

[Conventional technology]

Conventionally, there is a one-component primer composition composed of aminosilane and epoxysilane (for example, JP-A-56-62869).

In addition, A component composed of epoxy resin and aminosilane,
B consisting of epoxysilane, aminosilane and acid anhydride
There is also a primer composition composed of two liquids together with the components (for example, JP-A-56-34774).

[Problems to be solved by the invention]

However, the former primer composition has good adhesion to glassy substrates such as glass, tiles and pottery, but has insufficient adhesion to steel substrates. Further, when a solventless urethane anticorrosive paint is overcoated thereon, the adhesion between the primer and the overcoat will be poor unless the overcoat is applied within the same day after the primer is applied. That is, there is a problem that the coating interval of the primer is very short.

The latter primer composition has better adhesion to steel substrate than the former primer composition
There is a problem that the anticorrosion property is insufficient and the two-liquid type is inconvenient to use.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of diligent studies on a primer that is easy to use as a single liquid, having good water-resistant adhesiveness to a steel substrate, excellent anticorrosion properties, a long coating interval, and the like.

That is, the present invention relates to an epoxy resin [A] having two or more epoxy groups in one molecule, and an aliphatic amine having a molecular weight of 500 or less and one or more primary amino groups or secondary amino groups in one molecule. And / or a one-component primer containing a reaction product obtained by reacting an amine compound [B] which is an alicyclic amine and a monoepoxysilane [C] in a ratio satisfying the following formula (first invention). [However, (a ¹ ) is the number of moles of the epoxy resin [A] used,
(A ² ) is the number of epoxy groups in one molecule of the epoxy resin [A], (b ¹ ) is the number of moles of the amine compound [B] used, and (b ² )
Represents the number of hydrogen atoms directly bonded to the nitrogen atom in one molecule of the amine compound [B], and (c ¹ ) represents the number of moles of the monoepoxysilane [C] used. ] And a one-component primer containing a reaction product obtained by reacting the isocyanate compound [D] with each component of the first invention in a ratio satisfying the following formula (second invention). [However, (a ¹ ), (a ² ), (b ¹ ), (b ² ) and (c ¹ )
Is the same as in the first invention, (d ¹ ) represents the number of moles of the isocyanate compound [D] used, and (d ² ) represents the number of NCO groups in one molecule of the isocyanate compound [D]. ] And the one-component primer containing the metal powder in the above-mentioned first invention (third invention).

The epoxy resin [A] in the present invention contains two or more epoxy groups in one molecule, and specific examples thereof include the following.

(I) Bisphenol type epoxy resin Bisphenol A type epoxy resin, which is a condensate of bisphenols and epichlorohydrin, bisphenol F
Type epoxy resin, bisphenol S type epoxy resin and the like. For example, Epicort 828, Epicort 100
1. Epicoat 1007 (produced by Yuka Shell Co., Ltd.) and the like.

(Ii) Phenol type epoxy resin Novolak type epoxy resin in which epichlorohydrin acts on the initial condensate of novolac type phenol resin, resorcin type epoxy resin in which epichlorohydrin is condensed in the condensate of resorcin and acetone, and condensate of phenol and glyoxal Examples thereof include aromatic polyglycidyl type epoxy resins obtained by condensation of epichlorohydrin. For example, Epon 102, 1310 (manufactured by Nippon Kayaku Co., Ltd.)
Etc.

(Iii) Polyglycol type epoxy resin Polyglycols such as ethylene glycol, propylene glycol, and glycerin, which are reacted with epichlorohydrin, include glycerin triglycidyl (Epicoat 815, manufactured by Yuka Shell Co., Ltd.).

(Iv) Ester type epoxy resin Epicoat 872 (produced by Yuka Shell Co., Ltd.), which is a condensate of polycarboxylic acids and epichlorohydrin, can be mentioned.

(V) Cycloaliphatic Epoxy Resin Obtained by allowing peracetic acid to act on a cycloaliphatic unsaturated compound having two or more unsaturated groups. Is mentioned.

(VI) Si-containing epoxy resin as glycidyl silicon And so on.

Among these epoxy resins, bisphenol A type epoxy resin and novolac type epoxy resin are preferable, and they are excellent in water resistant adhesive to the base steel material.

Examples of the amine compound [B] include aliphatic amines and / or alicyclic amines having a molecular weight of 500 or less and having one or more primary amino groups or secondary amino groups in one molecule. Examples of the aliphatic amine include primary alkyl or cycloalkylamine such as methylamine, butylamine, octylamine, oleylamine, cyclopropylamine and cyclohexylamine, and polyethylenepolyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine as aliphatic polyamine. , Alkanolamines such as ethanolamine and diethanolamine, araliphatic polyamines such as diethyltoluenediamine and xylylenediamine, alicyclic polyamines such as cyclohexyldiamine and isophoronediamine, and heterocyclic polyamines such as piperazine. . Also,
Polyamides having a terminal amino group composed of these polyamines and polycarboxylic acids are also included. Of these, an aliphatic primary monoamine or an aliphatic polyamine is preferable.

The monoepoxysilane [C] has a general formula [In the formula, R ³ is a divalent hydrocarbon group, R ⁴ is an alkyl group or a phenyl group, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and n is 0 to
An integer of 1]. Specifically, as one having one glycidoxy group, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ −
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, γ-glycidoxypropyltriacetoxysilane, δ-glycidoxybutyltrimethoxysilane , Δ-glycidoxybutyltriethoxysilane, glycidoxymethyl (methyl) dimethoxysilane, glycidoxymethyl (ethyl) dimethoxysilane, glycidoxymethyl (phenyl) dimethoxysilane, glycidoxymethyl (vinyl) dimethoxysilane , Glycidoxymethyl (dimethyl) methoxysilane, β-glycidoxyethyl (methyl) dimethoxysilane, β-glycidoxyethyl (dimethyl) methoxysilane, γ-glycidoxypropyl (methyl) dimethoxysilane, γ-glycidoxyp Pyr (ethyl) dimethoxysilane, γ-glycidoxypropyl (dimethyl) methoxysilane, δ-glycidoxybutyl (methyl) dimethoxysilane, δ-glycidoxybutyl (ethyl) dimethoxysilane, δ-glycidoxybutyl ( Dimethyl) methoxysilane. As those having one glycidyl group, glycidylmethyltrimethoxysilane, glycidylmethyltriethoxysilane, β-glycidylethyltrimethoxysilane, β-glycidylethyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, γ-glycidylpropyl Triethoxysilane, γ-
Glycidylpropyltri (methoxyethoxy) silane,
gamma-glycidyl propyl triacetoxy silane is mentioned. The one having one alicyclic epoxy group is 3,
4-epoxycyclohexylmethyltrimethoxysilane, 3,4-epoxycyclohexylmethyltriethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, 3,4-epoxycyclohexylpropyltrimethoxysilane, 3,4-epoxycyclohexylbutyltriethoxysilane Mention may be made of methoxysilane.

In the present invention, the monoepoxy compound optionally used is allyl glycidyl ether, phenyl glycidyl ether, styrene oxide, n-butyl glycidyl ether, octylene oxide, propylene oxide, butylene used as a reactive diluent for epoxy resin. Examples thereof include oxide, dodecene oxide, methacryl glycidyl and the like.

The isocyanate compound [D] used in the present invention is
Aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, or urethane prepolymers and monoisocyanates having terminal NCO groups derived from these and polyols, polyamines are used.

As the aromatic polyisocyanate, diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, their dimers, trimers, modified polyisocyanates [polyisocyanates (such as MDI) carbodiimide group, uretdione group, Polyisocyanates modified to contain uretoimine groups (as described in JP-B-39-8968, JP-B-55-27098, JP-B-54-33597, etc.) such as ISONATE 143L (Chemical Upjohn )), Millionate MTL (manufactured by Hodogaya Chemical Co., Ltd.) and Sumidule PF, CD (manufactured by Sumitomo Bayer Urethane Co., Ltd.)]. Further, aliphatic polyisocyanates [hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate (HMDI), lysine diisocyanate, etc.], alicyclic polyisocyanates [isophorone diisocyanate, etc.] and dimers thereof,
Trimer, water-crosslinked polyisocyanate [Sumijour N-
75 (Sumitomo Bayer Urethane Co., Ltd.), Duranate 24
A-100 (Asahi Kasei Co., Ltd.)], polyol cross-linked NCO-terminated urethane prepolymer with a molecular weight of 200 or less [Duranate D
-201 (manufactured by Asahi Kasei Corporation)], and the monoisocyanate compound is ethyl isocyanate,
Phenyl isocyanate, toluene isocyanate, p
-Toluene sulfonyl isocyanate, trialkoxy silicon isocyanate, etc. are mentioned.

The preferred isocyanate compound [D] is an aliphatic or alicyclic polyisocyanate, or a monoisocyanate compound, and the particularly preferred monoisocyanate compound is trialkoxysilicon isocyanate.

The isocyanate compound [D] is used in the following cases. That is, the hydrogen atom directly bonded to the nitrogen atom in the amine compound [B] is replaced by the epoxy group of the epoxy resin [A] and the epoxy group in the monoepoxysilane [C], and the hydrogen atom directly bonded to the remaining nitrogen atom. Is substituted with an isocyanate compound to introduce a urea bond. Introducing a urea bond improves the adhesion between the primer and the urethane-based topcoat when the urethane-based topcoat is placed on the primer of the present invention.

In the present invention, the ratio of the epoxy resin [A] having two or more epoxy groups in one molecule, the amine compound [B], the monoepoxysilane [C] and the isocyanate compound [D] is calculated by the following formula. [However, (a ¹ ) is the number of moles of the epoxy resin [A] used,
(A ² ) is the number of epoxy groups in one molecule of the epoxy resin [A], (b ¹ ) is the number of moles of the amine compound [B] used, and (b ² )
Is the number of hydrogen atoms directly linked to the nitrogen atom in one molecule of the amine compound [B], (c ¹ ) is the number of moles of the monoepoxysilane [C] used, and (d ¹ ) is the number of moles of the isocyanate compound [D] used. , (D ² ) represents the number of NCO groups in one molecule of the isocyanate compound [D]. ] Within the range.

If the value of is less than 0.6, gelation tends to occur, and if it exceeds 2.5, the secondary adhesion (water resistant adhesion) decreases.

If the value of is less than 0.8, the secondary adhesion decreases, and if it exceeds 5.0, both the primary adhesion (adhesion during drying) and the secondary adhesion decrease.

A reaction procedure for making the epoxy resin [A], the amine compound [B] and the monoepoxysilane [C], or [A] to [C] and the isocyanate compound [D] into a one-component primer at a ratio within the above range. Is as follows.

(1) Epoxy resin [A] and amine compound [B] 10
Incubate for several hours at an optimum temperature of 0 ° C or less. Then, monoepoxysilane [C] is charged and allowed to react at an optimum temperature of 100 ° C. or lower for several hours. Further, if necessary, the isocyanate compound [D] is added at room temperature and the reaction is aged for several hours.

(2) The amine compound [B] and the monoepoxysilane [C] are reacted at an optimum temperature of 100 ° C. or lower for several hours. Then, the epoxy resin [A] is charged and allowed to react for several hours at an optimum temperature of 100 ° C. or lower. If necessary, a monoepoxy compound is added at room temperature and the reaction is aged for several hours at an optimum temperature of 100 ° C or lower.

(3) Epoxy resin [A], amine compound [B], and monoepoxysilane [C] are reacted at an optimum temperature of 100 ° C. or lower for several hours. Then, if necessary, the isocyanate compound [D] is added at room temperature and the reaction is aged for several hours.

The procedure of the above reaction is not particularly limited, and may be set according to the properties of the raw materials used so as not to cause gelation or insolubilization during the reaction.

Organic solvent, pigment, metal powder in the one-component primer of the present invention,
A plasticizer, an antioxidant, an anti-sagging agent, a curing catalyst and the like may be added.

Examples of the organic solvent include inert organic solvents such as aromatic hydrocarbon solvents (toluene, xylene, solvesso, etc.), ester organic solvents (ethyl acetate, butyl acetate, etc.), chlorine organic solvents (methylene dichloride, trichloroethylene, etc.) , Ether organic solvents (tetrahydrofuran, dioxane, etc.), ether ester organic solvents (methoxybutyl acetate, cellosolve acetate), ketone organic solvents (methyl ethyl ketone, methyl isobutyl ketone, etc.), aliphatic hydrocarbon organic solvents (hexane, minerals) Such as spirit) and mixed solvents thereof.

If necessary, a curing catalyst can be used in order to improve the low temperature curability and the drying property of the coating film. A tertiary amine compound is generally used as this catalyst. Examples of the tertiary amine compound include triethylamine, N-ethylmorpholine, triethylenediamine (DABCD), and 1,8-diaza-bicyclo (5.4.0) undecene-7 (DBU: manufactured by San Apot Co., Ltd.).

An anti-sagging agent can be added to impart anti-sagging property to the coating film. As this anti-sagging agent, ultra finely divided silica (Aerosil # 200, Aerosil # 300, etc.),
Synthetic wax (Day Spalon # 4200, Day Spalon # 30
1) and so on.

In the third invention, metal powder is used as a primer for steel materials in order to improve the corrosion resistance. Aluminum powder as metal powder,
Examples include zinc powder. Most preferred is zinc powder. As zinc powder, metallic zinc powder and metallic zinc alloy powder (Zn / A
1 alloy powder, Zn / Al / Mg alloy powder, etc.) are preferred, and metallic zinc powder is preferred. The particle size of zinc powder is usually 1 to 5 μm, and its shape is usually spherical. The amount of zinc powder used or blended in the dry coating film is usually 40 to 80%, preferably
50 to 70% by weight.

A pigment may be used in combination with the zinc powder, or only the pigment may be used. Usually, as the pigment, talc, mica, barium sulfate, glass powder, titanium oxide, red iron oxide, lead cyanamide, zinc chromate and the like are used.
These pigments are preferably surface-treated with a silane coupling agent in advance. When this treatment is performed, there are many advantages such as less adsorbed water on the surface of the pigment, good compatibility with the one-component primer of the present invention, easy increase in viscosity even if the pigment is highly blended, and easy workability. Is.

The formulation of the one-component primer of the present invention is as follows.

(1) Clear type Reaction product of the present invention 20 to 100 parts Organic solvent 80 to 0 parts Total 100 parts (2) Colored type reaction product of the present invention 20 to 80 parts Organic solvent 80 to 10 parts Anti-sagging agent 0.1 to 5 parts Anticorrosion pigment 0 to 20 parts Total 100 parts (3) Zinc rich type reaction product of the present invention 20 to 80 parts Organic solvent 50 to 10 parts Anti-sagging agent 0.1 to 5 parts Zinc powder 40 to 70 parts Total 100 parts The one-component primer of the present invention can be applied to various substrates. That is, cement-based substrates (concrete, mortar, slate, ALC, blocks, etc.), glass-based substrates (glass, tiles, ceramic pipes, etc.), clay-based substrates (brick, roof tiles, clay pipes, etc.), stone-based substrates (granite) , Marble, river sand, sea stones, etc.),
It can be applied to wood-based substrates (mostly wood, plywood, etc.) and metal-based substrates (structural steel, cast iron pipes, bolts / nuts, aluminum, etc.). In the case of a plastic base (PVC pipe, acrylic / melamine decorative plywood, urethane RIM bumper, etc.), the one-component primer of the present invention contains 10 to 10 parts of low molecular weight vinyl chloride, acrylic, styrene / butadiene copolymer as a film forming component. It can be applied by adding 20% by weight.

Silicone rubber, urethane rubber,
It can be applied as is to epoxy. In this way, it has good adhesion to various substrates and has a wide range of application. Especially, by using zinc-rich primer mixed with zinc powder for structural steel material, it becomes a primer that has anticorrosion property, excellent water resistance adhesiveness and low temperature curing property, and is one-component and easy to use. . Therefore, the zinc-rich primer for heavy-duty anticorrosion coating of large steel structures is more excellent than the conventional zinc-rich primer. When applied to such large steel structure substrates, it is generally necessary to use Sa2.5
The above sand plasting is performed, and the zinc rich primer in which zinc powder is mixed with the one-component primer of the present invention is applied by airless spraying to a film thickness of usually 30 to 100 μm. Then, an epoxy or urethane-based thick film top coating agent is applied to obtain a heavy anticorrosion coating aiming at long-term durability.

Since the one-component primer of the present invention has good water-resistant adhesion, it is easily affected by seawater and is used for offshore oil production platforms, seabers, special vessels (icebreakers, deep-sea research vessels, marine research vessels), large vessels (tankers). , Container ships, LNG carriers, military ships), large cold climate pipelines, marine cables, and primers for steel materials in large port facilities.

[Examples] Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Parts in the examples and comparative examples are parts by weight.

The details of the substances used in Examples and Comparative Examples are as follows.

Epoxy resin [A] Epicoat 828: Bisphenol A type epoxy resin. Epoxy equivalent of about 185 [made by Yuka Shell Co., Ltd.] Epicoat 1001: Bisphenol A type epoxy resin. Epoxy equivalent 487 [Yukaka Shell Co., Ltd.] Monoepoxysilane [C] KBM-402: γ-glycidoxypropylmethyldiethoxysilane [Shin-Etsu Chemical Co., Ltd.] KBM-403: γ-glycid Xypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Polyol Sannix diol PP-950: Polyether diol. O
HV = 118 [manufactured by Sanyo Kasei Co., Ltd.] Isocyanate compound [D] Polyisocyanate PAPI 135P: Crude MDI NCO = 31% [Kasei Upjohn Co., Ltd.]
Manufactured] Urethane primer GL primer: PPG / Coarse MDI type one-part moisture-curing urethane resin liquid. NV = 37%, NCO = 3.5% [manufactured by Sanyo Chemical Industry Co., Ltd.] Curing agent for epoxy resin React CA-200: Polyamidoamine, amine value ≈360 [manufactured by Sanyo Chemical Industry Co., Ltd.] Anti-sagging agent Ircogel 905: Calcium alkylbenzene sulfonate complex (manufactured by Lubrizol) Example 1 370 parts of Epicoat 828 and 120 of ethylenediamine in a reaction kettle
Parts, KBM-402 (992 parts) and methyl ethyl ketone (250 parts) were added, and the mixture was reacted at 50 ° C. for 5 hours. Then, after cooling to room temperature, 25 parts of ethanol was added and diluted to obtain a one-component primer [I].

Example 2 35 parts of the one-component primer [I] obtained in Example 1 and 60 parts of zinc powder
Part is kneaded with a closed kneader, and methyl ethyl ketone 5
Parts, and mixed and diluted to obtain a one-pack zinc rich primer [I].

Example 3 974 parts of Epicoat 1001 and methyl ethyl ketone part in a reaction kettle
Add 2131 parts and 228 parts of cyclohexyldiamine, 50 ℃
And reacted for 8 hours. Next, 826 parts of KBM-403 was added, and the mixture was reacted at 80 ° C. for 8 hours. After cooling to room temperature, 111 parts of isophorone diisocyanate was added, the temperature was gradually raised and the reaction was carried out at 50 ° C. for 3 hours to obtain a one-component primer [II].

Example 4 50 parts of the one-component primer [II] obtained in Example 3 and 50 parts of zinc powder
Parts and kneaded in a closed kneader to obtain a one-pack zinc rich primer [II].

Example 5 974 parts of Epikote 828, 146 parts of piperazine, and 1595 parts of methyl ethyl ketone were placed in a reaction kettle and reacted at 50 ° C. for 3 hours. Next, KBM-402 (496 parts) was added, the mixture was reacted at 80 ° C for 10 hours, cooled to room temperature, and then 26 parts of ethanol was added,
By mixing and diluting, one-component primer [III] was obtained.

Example 6 Zinc powder 1 was added to 50 parts of the one-pack primer [III] obtained in Example 5.
9 parts and 1 part of Ilcogel 905 were added and kneaded with a closed kneader. Next, add about 30 parts of one-component primer [III], knead and dilute it, and then use one-component zinc rich primer [III].
Got

Comparative Example 1 A reaction kettle was charged with 1970 parts of Sannix diol PP-950, 134 parts of trimethylolpropane, and 3904 parts of xylene.
The mixture was stirred and dissolved at ℃ for 1 hour. Then cool to room temperature,
Inject 1800 parts of PAPI 135P, gradually raise the temperature and make it 1 at 50 ° C.
The reaction was carried out at 80 ° C. for 8 hours to obtain a one-component urethane primer with NCO = 3.4%.

Comparative Example 2 30 parts of GL primer and 70 parts of zinc powder were kneaded in a closed kneader to give a one-pack urethane zinc rich primer.

Comparative Example 3 Epicoat 1001 487 parts and methyl ethyl ketone 156 parts 70 parts
It was dissolved by stirring at 0 ° C. for 1 hour to obtain an agent A. React CA
156 parts of -200 and 487 parts of methyl ethyl ketone were dissolved by stirring for 1 hour to prepare a B agent.

Agent A: Agent B = 1: 1 (weight ratio) to prepare a two-component epoxy primer.

Comparative Example 4 A two-component epoxy zinc rich primer was obtained by adding and dispersing 60 parts of zinc powder to 40 parts of the two-component epoxy primer, which was the mixture of agent A and agent B, obtained in Comparative Example 3.

Comparative Example 5 222 parts of KBM-403, 500 parts of KBM-402 and 500 parts of methyl ethyl ketone were put into a reaction vessel, reacted at 70 ° C. for 3 hours, then cooled to room temperature, and 222 parts of methanol was added to dilute the silane. A coupling agent primer was obtained.

Comparative Example 6 40 parts of the silane coupling agent primer obtained in Comparative Example 5 and 60 parts of zinc powder were kneaded with a closed kneader to obtain a silane coupling agent zinc rich primer.

Test Example 1 The primers of Examples 1, 3, 5 and Comparative Examples 1, 3, 5 were applied to various bases, various coating materials were applied, and the adhesion to the bases was evaluated. The results are shown in Table 1. Show.

It can be seen from Table 1 that the one-component primer of the present invention shows evenly good adhesiveness to various substrates, and is particularly excellent in water-resistant adhesiveness.

The test method of Table-1 is as follows.

Test No.1-1 The primer was applied once to the surface of a 30 x 30 x 5 cm sidewalk PC board with a brush and dried at 20 ° C for 1 day, then a commercially available epoxy floor material was applied to a thickness of 1.5 mm. Then, it was cured by curing at 20 ° C. for 1 week.

Vertical tensile test: In accordance with the Kenken tensile test JIS A-6910.

Test No.1-2 Cross section 12 × 1 with a formwork between two glass plates of 50 × 50 × 5mm
Make joints with a height of 2 mm and a height of 50 mm. A primer is applied to the ground surface of a glass plate, dried and cured at 20 ° C. for 1 day, and then a commercially available silicone sealant is filled in a mold joint using a knife and a caulking gun, taking care not to allow bubbles to enter. 20
An H-type test piece in which the silicone sealant was cured between two glass plates was prepared by curing and curing at 1 ° C. for 1 week.

Vertical tensile test: According to JIS A-5571.

Test No. 1-3 A primer was applied once to the surface of a piece of ceramic tubing with a brush, dried at 20 ° C for 1 day, and then a commercially available urethane sealant was applied to a thickness of 1.5 mm, followed by curing and curing at 20 ° C for 1 week. .

Peeling test: A urethane sealant layer and a primer layer were cut into a width of 1 cm with a cutter, and a 180 ° C peeling test was performed.

Test No. 1-4 Apply the primer once on the surface of the sandblasted steel plate with a brush and dry-cure for 1 day at 20 ° C. * Apply a urethane heavy anticorrosive paint with a thickness of 1 mm and cure at 20 ° C for 1 week. did.

Vertical Tensile Test: A vertical test was conducted using an adhesion tester (Elkometer).

* Two-component reactive urethane-based heavy-duty anticorrosion paint: Samprene SK-600
[Made by Sanyo Kasei Co., Ltd.] Test No. 1-5 Cross section 12 × 1 with a formwork between two aluminum plates of 50 × 50 × 5 mm
Make joints with a height of 2 mm and a height of 50 mm. A primer is applied to the surface of an aluminum plate and dried and cured at 20 ° C. for 1 day. Then, a commercially available modified silicone thin sealant is used to fill a mold joint with a knife and a caulking gun, taking care not to allow air bubbles to enter. After curing for 1 week at 20 ° C., an H-shaped test piece in which the modified silicone sealant was cured between two aluminum plates was prepared.

Vertical tensile test: According to JIS A-5571.

Test No. 1-6 A primer: calcium carbonate 2: 1 mixture was applied to the surface of plywood to obtain a primer having a sealing effect. After drying and curing at 20 ° C. for 1 day, a commercial acrylic urethane paint was spray-coated and cured at 20 ° C. for 1 week.

Cross-section test: Cross-cut with a knife at a width of 1 mm, after sticking an adhesive tape, it was peeled off and evaluated by how many squares were peeled out in 100 squares.

Test No. 2 The zinc-rich primer of Examples 2, 4 and 6 and Comparative Examples 2, 4 and 6 and a commercial zinc-rich primer applied to a sandblasted steel plate, and a heavy anticorrosive paint applied on it Table 2 shows the results of evaluation of the properties, adhesiveness and impact resistance.

From Table-2, it can be seen that the one-component primer of the present invention is excellent in corrosion resistance, water-resistant adhesion and impact resistance against the steel substrate.

Comparative Example A is a commercially available inorganic zinc rich primer, Comparative Example B
Is a commercially available epoxy zinc rich primer.

Test Example 3 The zinc-rich primer of Examples 2, 4, 6 and Comparative Examples 2, 4, 6 and a commercial primer were applied to a sandblasted steel sheet, and the coating interval (time interval between primer coating and topcoat coating) was changed to achieve adhesiveness. The results of evaluation of are shown in Table-3.

From Table-3, the one-component primer of the present invention has a wide coating interval, and thus is suitable as a primer for on-site construction.
In Table 3, Comparative Example A, Comparative Example B, used top coat, adhesive strength (primary adhesion) evaluation level ◯ mark, Δ mark, X mark and measuring method are the same as in Test Example 2.

[Effect of the Invention] The one-component primer of the present invention has the following effects as compared with the conventional primer composition.

(1) It shows evenly good adhesiveness to various substrates and exhibits adhesiveness to all substances. (2) It has excellent water-resistant adhesiveness without significantly reducing adhesion after immersion in water.

(3) When zinc powder is blended into a zinc-rich primer, it becomes a primer excellent in anticorrosion property, and is suitable as a primer for heavy anticorrosion paint.

(4) Even after 7 days from the primer application, sufficient adhesiveness is exhibited even if the top coat is applied, so the coating interval is long and it is easy to use.

(5) Particularly excellent in low temperature curability, and can be used even at 0 to -5 ° C.

(6) It becomes a high solid type, and thick film primer coating is possible. Therefore, the anticorrosion performance of the primer layer is further improved.

Since the one-component primer of the present invention has the above effect,
In particular, it is highly promising as a thick film primer for heavy-duty anticorrosion paints aimed at maintenance-free of large steel structures.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Takagaki, 1-1-15 Toyosu, Koto-ku, Tokyo Ishikawajima Harima Heavy Industries Ltd. Technical Research Institute (72) Inventor Takeyoshi Komori 11-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Prefecture No. 1 Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Shuji Ono No. 1 Hitotsubashi Honcho, Higashiyama-ku, Kyoto City, Kyoto Prefecture No. 1 Sanyo Kasei Kogyo Co., Ltd. (56) Reference JP-A-51-34222 (JP, A) Kai 61-274766 (JP, A) JP 57-127479 (JP, A) JP 57-53524 (JP, A)

Claims (10)

[Claims] 1. An epoxy resin [A] having two or more epoxy groups in one molecule, an aliphatic amine having a molecular weight of 500 or less and having one or more primary amino groups or secondary amino groups in one molecule, and A one-component primer containing a reaction product obtained by reacting an amine compound [B] which is an alicyclic amine and / or a monoepoxysilane [C] at a ratio satisfying the following calculation formula. [However, (a ¹ ) is the number of moles of the epoxy resin [A] used,
(A ² ) is the number of epoxy groups in one molecule of the epoxy resin [A], (b ¹ ) is the number of moles of the amine compound [B] used, and (b ² )
Represents the number of hydrogen atoms directly bonded to the nitrogen atom in one molecule of the amine compound [B], and (c ¹ ) represents the number of moles of the monoepoxysilane [C] used. ] 2. The epoxy resin [A] has the general formula [In the formula, R ¹ and R ² are hydrogen, a methyl group, an ethyl group or CF ₃
Group, n is an integer of 0 to 9] or the general formula A one-component primer according to claim 1, wherein n is an integer of 0 to 10. 3. A monoepoxysilane [C] is represented by the general formula [In the formula, R ³ is a divalent hydrocarbon group, R ⁴ is an alkyl group or a phenyl group, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and n is 0 to
An integer of 1], Claim 1 or 2
The one-component primer according to the item. 4. An epoxy resin [A] having two or more epoxy groups in one molecule, an aliphatic amine having a molecular weight of 500 or less and one or more primary amino groups or secondary amino groups in one molecule, and / Or one-component primer containing a reaction product obtained by reacting an amine compound [B] which is an alicyclic amine, a monoepoxysilane [C] and an isocyanate compound [D] in a ratio satisfying the following calculation formula. . [However, (a ¹ ) is the number of moles of the epoxy resin [A] used,
(A ² ) is the number of epoxy groups in one molecule of the epoxy resin [A], (b ¹ ) is the number of moles of the amine compound [B] used, and (b ² )
Is the number of hydrogen atoms directly linked to the nitrogen atom in one molecule of the amine compound [B], (c ¹ ) is the number of moles of the monoepoxysilane [C] used, and (d ¹ ) is the number of moles of the isocyanate compound [D] used. , (D ² ) represents the number of NCO groups in one molecule of the isocyanate compound [D]. ] 5. The epoxy resin [A] has the general formula [In the formula, R ¹ and R ² are hydrogen, a methyl group, an ethyl group or CF ₃
Group, n is an integer of 0 to 9] or the general formula A one-component primer according to claim 4, wherein n is an integer of 0 to 10. 6. A monoepoxysilane [C] is represented by the general formula [In the formula, R ³ is a divalent hydrocarbon group, R ⁴ is an alkyl group or a phenyl group, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and n is 0 to
An integer of 1], Claim 4 or 5
The one-component primer according to the item. 7. The one-component primer according to claim 4, wherein the isocyanate compound [D] is a monoisocyanate or an aliphatic or alicyclic polyisocyanate. 8. An epoxy resin [A] having two or more epoxy groups in one molecule, an aliphatic amine having a molecular weight of 500 or less and one or more primary amino groups or secondary amino groups in one molecule, and And / or a one-component primer containing a reaction product obtained by reacting an amine compound [B] that is an alicyclic amine and a monoepoxysilane [C] in a ratio that satisfies the following calculation formula, and a metal powder. [However, (a ¹ ) is the number of moles of the epoxy resin [A] used,
(A ² ) is the number of epoxy groups in one molecule of the epoxy resin [A], (b ¹ ) is the number of moles of the amine compound [B] used, and (b ² )
Represents the number of hydrogen atoms directly bonded to the nitrogen atom in one molecule of the amine compound [B], and (c ¹ ) represents the number of moles of the monoepoxysilane [C] used. ] 9. The epoxy resin [A] has the general formula [In the formula, R ¹ and R ² are hydrogen, a methyl group, an ethyl group or CF ₃
Group, n is an integer of 0 to 9] or the general formula The one-component primer according to claim 8, which is represented by [wherein n is an integer of 0 to 10]. 10. A monoepoxysilane [C] has the general formula [In the formula, R ³ is a divalent hydrocarbon group, R ⁴ is an alkyl group or a phenyl group, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and n is 0 to
An integer of 1], Claims 8 or 9
The one-component primer according to the item.